CN1134510C - Bitumen compositions and a process for their preparation - Google Patents
Bitumen compositions and a process for their preparation Download PDFInfo
- Publication number
- CN1134510C CN1134510C CNB961986220A CN96198622A CN1134510C CN 1134510 C CN1134510 C CN 1134510C CN B961986220 A CNB961986220 A CN B961986220A CN 96198622 A CN96198622 A CN 96198622A CN 1134510 C CN1134510 C CN 1134510C
- Authority
- CN
- China
- Prior art keywords
- block
- pitch
- mixture
- bituminous composition
- comonomers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/30—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by mixing gases into liquid compositions or plastisols, e.g. frothing with air
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L95/00—Compositions of bituminous materials, e.g. asphalt, tar, pitch
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2395/00—Bituminous materials, e.g. asphalt, tar or pitch
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Road Paving Structures (AREA)
Abstract
The invention provides a process for preparing a bitumen composition comprising blowing a mixture with an oxygen-containing gas which mixture comprises a bitumen having a penetration of less than 300 dmm (as measured by ASTM D 5 at 25 DEG C) and a thermoplastic rubber which is present in an amount of less than 5 wt.%, based on total mixture; bitumen compositions obtainable by such process; and the use of such bitumen compositions in asphalt mixtures for road applications.
Description
The present invention relates to bituminous composition, their preparation method, and their application in road construction usefulness pitch (asphalt) mixture.
Pitch is used as tackiness agent in the road asphalt mixtures, and is constantly developing, to adapt to the performance requriements that growing road building is used.In road pitch, the bituminous performance is good usually, but ever-increasing heavy traffic loading has caused the premature breakage of a lot of roads, shows as the cracking on rut seal and surface.Cracking is a major defect on asphalt road, because it makes water enter the bottom of road surfaces, causes the rapid corruption of bottom, and has quickened too early maintenance.Increase the content of pitch medium pitch or use softer other pitch of level, can improve bituminous splitting resistance under the low temperature, but because mixture is softer relatively, so at high temperature be easy to produce the rut seal.On the contrary, usage quantity or hard other pitch of level of use by reducing the pitch medium pitch can improve anti-rut seal property, but cost are to lose splitting resistance, because the reduction of the snappiness of mixture.
In sum, as can be seen, be starved of a kind of hard pitch composition of development to adapt to the needs of splitting resistance now, promptly bituminous composition should have good low-temperature performance, and the anti-rut seal property of good high-temperature is arranged simultaneously again.
Can to improve the bituminous low-temperature performance be known by sneaking into polymkeric substance.Yet when this modification is applied to hard pitch, observe the incompatible behavior between pitch and polymkeric substance usually, cause being difficult to maybe can't improve low-temperature performance, and cause relatively poor relatively ageing-resistant performance.
Further be well known that by WO94/16019, carry out common blowing, can prepare industrial and roof construction other pitch of level by making the bitumen/polymer mixture.As if yet these bituminous compositions are unsuitable for road and use, reason is their softening temperature height, and penetration degree is higher relatively.
The purpose of this invention is to provide a kind of bituminous composition that road is used that is suitable for, this bituminous composition had both had good low-temperature performance, had the anti-rut seal property of good high-temperature simultaneously again, had improved ageing-resistant performance in addition.
Now be surprised to find, blow (blow), can prepare this bituminous composition by making specific asphalt mixture.
In view of the above, the present invention relates to a kind of method for preparing bituminous composition, comprise the gas blowing mixture that contains oxygen with a kind of, this mixture contains penetration degree and is the pitch less than 300dmm (pressing ASTM D 5 tests down for 25 ℃), and based on the amount of whole mixtures, content is less than the thermoplastic elastomer of 5 weight %.
Aptly, based on the amount of whole mixtures, the amount of thermoplastic elastomer is less than 3 weight %, is preferably 1～3 weight %.
The penetration of bitumens that is used for the inventive method is less than 300dmm (pressing ASTM D 5 tests down for 25 ℃).
Aptly, penetration of bitumens is less than 250dmm, preferably less than 200dmm (pressing ASTM D 5 tests down for 25 ℃).
Blowing is with containing the gas of oxygen, carries out as air or pure oxygen.The preferred air that uses.
Aptly, method of the present invention is carried out in 200～280 ℃ temperature range.
Preferably, method of the present invention is carried out under 210～260 ℃, more preferably 230～250 ℃.
Can under environmental stress or high pressure, carry out according to method of the present invention.Yet it carries out under environmental stress usually.
Aptly, method of the present invention is less than 4 hours, preferably less than 3 hours, is more preferably less than in 2.5 hours the time range and carries out.
Contain a kind of thermoplastic elastomer in this mixture.Also can contain one or more dissimilar thermoplastic elastomers in this mixture.Yet preferably, only use one type thermoplastic elastomer.
Although the thermoplastic elastomer that can suit to use according to the present invention has a lot, preferred thermoplastic elastomer comprises the segmented copolymer of selective hydration, wherein contains at least two poly-monovinylarene blocks of end and polymerized conjugated diene block in the middle of at least one.
It is A (BA) that preferred segmented copolymer formation is selected from general formula
mOr (AB)
nThose of X, wherein A represents to be essentially the block of poly-monovinylarene, and B represents to be essentially the block of polymerized conjugated diene, X represents the residue of multivalence coupling agent, and n represents more than or equal to 1, is preferably greater than to equal 2 integer, m represents the integer more than or equal to 1, and preferred m is 1.
More preferably, block A represents to be essentially the block of polystyrene, and B represents to be essentially the block of polyhutadiene or polyisoprene.The multivalence coupling agent comprises the coupling agent that those this areas are commonly used.
Term " basically " is meant that block A and B mainly are derived from mono vinyl arenes monomer and conjugate diene monomer respectively, these monomers can be mixed with other close or not close on structure comonomer, for example mono vinyl arenes monomer is as main component, and also contain a spot of other monomer (at the most 10%), or divinyl is mixed with isoprene, or is mixed with a spot of vinylbenzene.
More preferably, these multipolymers contain pure polystyrene, pure polyisoprene or pure polybutadiene block, and wherein polyisoprene or polybutadiene block can be hydrogenated to remaining olefinic degree of unsaturation by selectivity and be at most 20%, most preferably less than 5%.Most preferably, the structure of used segmented copolymer is ABA, and wherein the apparent molecular weight of A is 3000 to 100000, and is preferred 5000 to 40000, and the apparent molecular weight of B is 10000 to 250000, preferred 40000 to 200000.The polymerized conjugated diene block of initial preparation contains the vinyl of 5～50 moles of % usually, and this vinyl is derived from 1 of conjugated diolefine molecule, the 2-polymerization, and preferred vinyl content is 10～25%.
By whole segmented copolymers used in the present invention, the polymeric vinyl aromatic monomer that contains usually is 10～60 weight %, preferred 15～45 weight %.
The apparent molecular weight of whole segmented copolymer is generally 15000 to 350000, and preferred 40000 to 250000.
Example as suitable pure segmented copolymer, that can mention has KRATON G-1651, KRATON G-1654, a KRATON G-1657, KRATON G-1650, KRATON G-1701, KRATON D-1101, KRATON D-1102, KRATON D-1107, KRATON D-1111, KRATON D-1116, KRATON D-1117, KRATON D-1118, KRATON D-1122, KRATON D-1135X, KRATON D-1184, KRATON D-1144X, KRATON D-1300X, KRATON D-4141 and KRATON D-4158 (KRATON is a trade mark).
Pitch can be the resistates of crude distillation, and the cracking resistates is by the resistates of crude oil or crude distillation resistates or former oil extract blowing (blow) gained, from the pitch of propane pitch, butane pitch, pentane pitch or its mixture.Other suitable pitch comprises above-mentioned pitch and extending oil (fluxing oil) as the oil extract, for example the mixture of aromatic series extract, product of distillation or resistates.
Aptly, used bituminous softening temperature is 35～65 ℃, preferred 42～58 ℃ (ten thousand methods of pressing ASTM D 36 are measured).
A very wondrous and aspect that have an advantage of the present invention is, can need not to use pitch blowing catalyzer, and under the condition of gentleness the very attracting bituminous composition of preparation.Therefore, according to method of the present invention, aptly, under no pitch blowing catalyzer, carry out.
Above-mentioned thermoplastic elastomer is preferably the thermoplastic elastomer of unvulcanised.According to the present invention, use the advantage of unvulcanised thermoplastic elastomer to be, can need not to use vulcanizing agent and make very attracting bituminous composition.Therefore, method of the present invention can suit to carry out in the presence of no vulcanizing agent.
To understand as those skilled in the art, the mixture of pitch and thermoplastic elastomer preheated earlier before blowing.The mixture of pitch and thermoplastic elastomer is normally pre-warmed like this, makes that promptly the temperature of original mixture is 160～220 ℃.
In addition, the present invention also provides the bituminous composition that can be obtained by above-mentioned arbitrary method.Aptly, the penetration degree of this bituminous composition is less than 100dmm, preferably less than 75dmm (pressing ASTM D 5 tests down for 25 ℃), its softening temperature is 60～90 ℃, preferred 65～75 ℃ (press ASTMD 36 method measure), and based on the amount of whole bituminous compositions, said composition contains less than 5 weight %, preferably less than 3 weight %, any above-mentioned thermoplastic elastomer of 1～3 weight % more preferably.This bituminous composition is very attracting, because it had both had good low-temperature performance, has the anti-rut seal of good high-temperature performance simultaneously again.
Employed filler such as carbon black in the bituminous composition, silicon-dioxide and lime carbonate, stablizer, oxidation inhibitor, pigment and solvent are known, they in the present composition and also be well known in the art with concentration.
The present invention also further relates to the application of above-mentioned bituminous composition in road construction usefulness asphalt mixtures.
To further specify the present invention by embodiment below.
Embodiment 1
Based on a kind of penetration degree is pitch and a kind of industrial non-naphthenic asphalt that is made through distillation by crude oil of 100 (pressing ASTM D 5 tests down for 25 ℃), prepares a kind of mixture.This bituminous penetration index is 0.5, and softening temperature is 44 ℃ (method of pressing ASTM D 36 is measured).Based on the amount of whole mixtures, in this pitch, add a kind of segmented copolymer of 2 weight %.Its polymers of used block is its polymers of hydrogenant polystyrene-poly divinyl-polystyrene block, and its styrene content is 30 weight %, is standard substance with the polystyrene, and recording its number-average molecular weight by GPC is 103000.The olefinic degree of unsaturation of this polymkeric substance is reduced to less than 1% of its initial degree of unsaturation by hydrogenation.
This mixture is by 180 ℃ of following blend pitches and segmented copolymer preparation.Subsequently, in blown container, use air blown 2 hours in 220 ℃ of mixtures that preheat with gained.The salient features of the oxidized bitumen composition of gained is listed in the table 1.
Embodiment 2
To compare blowing as embodiment 1 described similar fashion, different is not add thermoplastic elastomer in the pitch.The salient features of gained oxidized bitumen is listed in the table 1.
The bituminous composition of gained is carried out roll-in thin film oven test (ASTM testing method D2572).The salient features of the bituminous composition behind this burn-in test is listed in the bottom of table 1.
Embodiment 3
To compare blowing as embodiment 1 described similar fashion, different is after the pitch blowing, adds segmented copolymer in pitch.The salient features of the oxidized bitumen composition of gained is listed in the table 1.
Embodiment 4
Blowing as embodiment 1 described similar fashion, the different amounts that is based on whole mixtures, the segmented copolymer that adds in the pitch is 1 weight %.The salient features of the oxidized bitumen composition of gained is listed in the table 1.
The salient features of the bituminous composition after having carried out the RTFOT burn-in test is listed in the bottom of table 1.
Can clearly be seen that by the result shown in the table 1, according to method of the present invention (embodiment 1 and 4), can prepare hard pitch composition with very attracting low temperature elasticity, as passing through shown in the Fraass breaking point (measuring) by IP 80, and blow according to the method outside the scope of the invention (embodiment 2 and 3), the hard pitch goods that then obtain are just so not attractive.And, can be clear that by embodiment 2 and 4 bituminous composition of the present invention is more stable to thermooxidizing.
| Embodiment | 1 | 2 | 3 | 4 |
| Form thermoplastic elastomer (weight %) | 2 | 0 | 2 | 1 |
| 25 ℃ of the performance penetration degree of 220 ℃ of blowings after 2 hours, (0.1mm) softening temperature ring and ball, (℃) penetration index, (-) Fraass breaking point, (℃) | 24 67.5 0.7 -13 | 20 65 0.0 -5 | 16 81 1.9 -2 | 25 63 0.1 -10 |
| Needle penetration (%) the softening point ring of 25 ℃ of (0.1mm) reservations of the performance needle penetration behind the RTFOT burn-in test and ball (℃) the softening point increase (℃) penetration index (-) Fraas breaking point (℃) | 16 80 72 7 0.7 -3 | 21 84 65.5 2.5 0.2 -7 |
Claims (8)
1. one kind prepares and is used for the method for road construction with the bituminous composition of asphalt mixtures, comprise the gas blowing mixture that contains oxygen with a kind of, this mixture contains the pitch of penetration degree less than 300dmm (pressing ASTM D5 test down for 25 ℃), and based on the amount of whole mixtures, content is less than the thermoplastic elastomer of 5 weight %.
2. the process of claim 1 wherein the mixture air blown.
3. claim 1 or 2 method, wherein used temperature is 210～260 ℃.
4. each method of claim 1 to 3, wherein thermoplastic elastomer comprises the segmented copolymer of selective hydration, this multipolymer contains at least two poly-monovinylarene blocks of end and polymerized conjugated diene block in the middle of at least one.
5. the method for claim 4, wherein the general formula of segmented copolymer is A (BA)
mOr (AB)
nX, wherein A represents the block of poly-monovinylarene and maximum 10% comonomers, and B represents the block of polymerized conjugated diene and maximum 10% other comonomers, and X represents the residue of multivalence coupling agent, and n represents the integer more than or equal to 1, m represents the integer more than or equal to 1.
6. the method for claim 5, wherein the A block is the block of polystyrene and maximum 10% other comonomers, the B block is the block of polyhutadiene or polyisoprene and maximum 10% other comonomers.
7. by each the bituminous composition that method obtained of claim 1 to 6.
8. the application of the bituminous composition of claim 7 in road construction usefulness asphalt mixtures.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP95308548 | 1995-11-28 | ||
| EP95308548.7 | 1995-12-11 | ||
| EP95402789 | 1995-12-11 | ||
| EP95402789.2 | 1995-12-11 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1202920A CN1202920A (en) | 1998-12-23 |
| CN1134510C true CN1134510C (en) | 2004-01-14 |
Family
ID=26140471
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB961986220A Expired - Fee Related CN1134510C (en) | 1995-11-28 | 1996-11-27 | Bitumen compositions and a process for their preparation |
Country Status (21)
| Country | Link |
|---|---|
| EP (1) | EP0863947B1 (en) |
| JP (1) | JP2000500801A (en) |
| KR (1) | KR19990071485A (en) |
| CN (1) | CN1134510C (en) |
| AP (1) | AP1005A (en) |
| AT (1) | ATE195756T1 (en) |
| AU (1) | AU702539B2 (en) |
| CA (1) | CA2237904A1 (en) |
| CZ (1) | CZ164198A3 (en) |
| DE (1) | DE69609986T2 (en) |
| DK (1) | DK0863947T3 (en) |
| ES (1) | ES2149513T3 (en) |
| GR (1) | GR3034851T3 (en) |
| HK (1) | HK1010556A1 (en) |
| NZ (1) | NZ323926A (en) |
| PL (1) | PL326984A1 (en) |
| PT (1) | PT863947E (en) |
| SI (1) | SI0863947T1 (en) |
| SK (1) | SK282693B6 (en) |
| TR (1) | TR199800932T2 (en) |
| WO (1) | WO1997019997A2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2318121A (en) * | 1996-10-11 | 1998-04-15 | Shell Int Research | Bituminous compositions and a process for their preparation |
| US7576148B2 (en) * | 2005-11-09 | 2009-08-18 | Kraton Polymers U.S. Llc | Blown asphalt compositions |
| JP4856460B2 (en) * | 2006-03-31 | 2012-01-18 | 昭和シェル石油株式会社 | Asphalt composition |
| JP6300749B2 (en) * | 2015-03-20 | 2018-03-28 | Ｊｘｔｇエネルギー株式会社 | Rigid asphalt composition, goose asphalt mixture and method for producing them |
| JP6545059B2 (en) * | 2015-09-29 | 2019-07-17 | 昭和シェル石油株式会社 | Polymer modified asphalt composition |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE2115475C3 (en) * | 1971-03-31 | 1980-03-27 | Deutsche Bp Ag, 2000 Hamburg | Process for improving the properties of mixtures of bitumen and / or related substances |
| US5342866A (en) * | 1992-12-30 | 1994-08-30 | Owens-Corning Fiberglas Technology Inc. | Oxidized asphalt rubber system |
-
1996
- 1996-11-27 JP JP9520197A patent/JP2000500801A/en not_active Ceased
- 1996-11-27 CN CNB961986220A patent/CN1134510C/en not_active Expired - Fee Related
- 1996-11-27 SI SI9630200T patent/SI0863947T1/en unknown
- 1996-11-27 PT PT96941651T patent/PT863947E/en unknown
- 1996-11-27 SK SK699-98A patent/SK282693B6/en unknown
- 1996-11-27 CA CA002237904A patent/CA2237904A1/en not_active Abandoned
- 1996-11-27 PL PL96326984A patent/PL326984A1/en unknown
- 1996-11-27 WO PCT/EP1996/005365 patent/WO1997019997A2/en not_active Application Discontinuation
- 1996-11-27 KR KR1019980703757A patent/KR19990071485A/en active IP Right Grant
- 1996-11-27 NZ NZ323926A patent/NZ323926A/en unknown
- 1996-11-27 AP APAP/P/1998/001242A patent/AP1005A/en active
- 1996-11-27 AT AT96941651T patent/ATE195756T1/en not_active IP Right Cessation
- 1996-11-27 CZ CZ981641A patent/CZ164198A3/en unknown
- 1996-11-27 AU AU10973/97A patent/AU702539B2/en not_active Ceased
- 1996-11-27 DK DK96941651T patent/DK0863947T3/en active
- 1996-11-27 ES ES96941651T patent/ES2149513T3/en not_active Expired - Lifetime
- 1996-11-27 EP EP96941651A patent/EP0863947B1/en not_active Expired - Lifetime
- 1996-11-27 DE DE69609986T patent/DE69609986T2/en not_active Expired - Fee Related
- 1996-11-27 TR TR1998/00932T patent/TR199800932T2/en unknown
-
1998
- 1998-11-03 HK HK98111700A patent/HK1010556A1/en not_active IP Right Cessation
-
2000
- 2000-11-15 GR GR20000402540T patent/GR3034851T3/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| DK0863947T3 (en) | 2000-10-30 |
| CN1202920A (en) | 1998-12-23 |
| AP1005A (en) | 2001-08-06 |
| GR3034851T3 (en) | 2001-02-28 |
| DE69609986T2 (en) | 2001-03-15 |
| ES2149513T3 (en) | 2000-11-01 |
| ATE195756T1 (en) | 2000-09-15 |
| DE69609986D1 (en) | 2000-09-28 |
| WO1997019997A3 (en) | 1997-07-03 |
| NZ323926A (en) | 1999-08-30 |
| SK282693B6 (en) | 2002-11-06 |
| AU1097397A (en) | 1997-06-19 |
| CA2237904A1 (en) | 1997-06-05 |
| EP0863947B1 (en) | 2000-08-23 |
| AP9801242A0 (en) | 1998-06-30 |
| KR19990071485A (en) | 1999-09-27 |
| AU702539B2 (en) | 1999-02-25 |
| SK69998A3 (en) | 1998-10-07 |
| HK1010556A1 (en) | 1999-06-25 |
| PT863947E (en) | 2001-01-31 |
| PL326984A1 (en) | 1998-11-09 |
| WO1997019997A2 (en) | 1997-06-05 |
| CZ164198A3 (en) | 1998-09-16 |
| SI0863947T1 (en) | 2000-12-31 |
| TR199800932T2 (en) | 1998-08-21 |
| JP2000500801A (en) | 2000-01-25 |
| EP0863947A2 (en) | 1998-09-16 |
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| C14 | Grant of patent or utility model | ||
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| C19 | Lapse of patent right due to non-payment of the annual fee | ||
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